US2859247A - Process for the preparation of bicyclic ketones - Google Patents
Process for the preparation of bicyclic ketones Download PDFInfo
- Publication number
- US2859247A US2859247A US470797A US47079754A US2859247A US 2859247 A US2859247 A US 2859247A US 470797 A US470797 A US 470797A US 47079754 A US47079754 A US 47079754A US 2859247 A US2859247 A US 2859247A
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- oxidation
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims description 22
- 230000008569 process Effects 0.000 title claims description 21
- -1 bicyclic ketones Chemical class 0.000 title description 14
- 238000002360 preparation method Methods 0.000 title description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 10
- 230000005587 bubbling Effects 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 5
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002432 hydroperoxides Chemical class 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- JBXIOAKUBCTDES-UHFFFAOYSA-N 2h-acenaphthylen-1-one Chemical compound C1=CC(C(=O)C2)=C3C2=CC=CC3=C1 JBXIOAKUBCTDES-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 150000007659 semicarbazones Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- NDVAMUMVOJRAJV-UHFFFAOYSA-N 10h-phenanthren-9-one Chemical compound C1=CC=C2C(=O)CC3=CC=CC=C3C2=C1 NDVAMUMVOJRAJV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXPBFNVKTVJZKF-UHFFFAOYSA-N dihydrophenanthrene Natural products C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
- C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
- C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
Definitions
- the present invention relates to a process for the preparation of bicyclic ketones.
- the reaction is a chain reaction yielding, as first isolatable products, hydroperoxides of the formula ROOH, wherein R stands for ahydrocarbon radical, the subsequent selective decomposition of which gives the desired oxygenated compounds, either directly or by way of complex reactions.
- the primary objects of the present invention are:
- atomization device may advantageously be made of an atomization device of any suitable and per se conventional construction.
- reaction temperature between C. and 200 C., either by cooling or by supplying the necessary amount of heat over and above that already furnished by the reaction itself. Too low a temperature favors accumulation of hydroperoxides; too high a temperature reduces the yield because of the formation of secondary-products.
- the process according to the invention is characterized by the simultaneous employment, for the said hydrocarbons, of oxidation catalysts and of acid solvents which serve not only to decrease the induction period and to increase the speed of the selective reaction for the formation of the corresponding ketones, but also to reduce the content of hydroperoxides to a negligible value.
- the catalysts thus employed are cations of metals such as vanadium, chromium, manganese, copper, zinc, silver,
- tin, antimony, lead, bismuth, iron, nickel and cobalt are formed upon the dissolution of the metals or of an oxide or salt (for example chloride, nitrate, sulfate, etc.) of the said metals or of a soap (for example acetate, propionate, palmitate, stearate, naphthenate, etc.) of such metals, in the aforementioned acid solvent.
- concentration of catalysts relative to hydrocarbon can be reduced, according to this invention, down to very low values of the order of for example however, this figure is not at all intended to be lirnitative, since other concentrations may be employed.
- the acid solvents which can be employed according to the invention are straight-chain or branched-chain monobasic organic acids, particularly lower alk anoic acids, preferably acetic acid, propionic acid and butyric acid.
- the molar hydrocarbon solvent proportion of the hydrocarbon-solvent mixtures employed according to the invention be within the range V30 f0 20. employed.
- thermocouple may advantageously be employed for observing the temperature.
- Typical presently-preferred embodiments of the invention are set forth, by way of illustration, in the examples which follow. In such examples, the temperatures are set forth in degrees centigrade. Parts by weight" bear the same relation to parts by volume as do grams tov milliliters. Percentages are by weight.
- Example 1 A mixture of 583 parts by weight of tetralin (tetrahydronaphthalene), 315 parts by weight of acetic acid,
- CoCl- preliminarily dissolved in the acetic acid
- the oxidation apparatus which may conveniently be of Other molar proportions may, however, be
- the authenticity of the a-tetralone is confirmed inter alia by conversion thereof into the oxime and semi-carbazone and by its refractive index.
- oxygen-in this example as well as in those which follow. may also conveniently be supplied in the form of an oxygen-containing gas, such as air.
- Example 2 A mixture of 398 parts by weight of Tetralin, 176 parts by Weight of acetic acid, and 0.2 part by weight of manganous acetate (previously dissolved in the acetic acid) is introduced into the reaction vessel, and oxidation carried out after-the manner described in Example 1 for a period of 65 minutes at a temperature of 110.
- Example 3 A mixture of 398 parts by weight of Tetralin (3 mol.), 176 parts by weight of acetic acid and 0.2 part by weight of Ni(OH) (previously dissolved in the acetic acid) is introduced into-the reaction vessel and oxidation carried out after the manner described in Example 1 for a period of 75 minutes at a temperature of 125 C.
- the authenticity of the a-tetralone is confirmed inter alia by conversion thereof into the oxime and semicarbazone.
- Example 4 A mixture of 396 parts by weight of Tetralin, 222 parts by weight of propionic acid and 0.2 part by weight of CoCl (previously dissolved in the acetic acid) is intro dragonacted into the reaction vessel and oxidation carried out after the manner described in Example 1 for a period of 65 minutes at a temperature of 100 C.
- the resultant mixture contains less than 1% of peroxide.
- 297 parts by weight of unreacted Tetralin'and 388 parts by weight of tetralone (which represents a 76% molar yield relative to the reacted Tetralin) are recovered.
- Example 6 A mixture of 175 parts by weight of indane, 88 parts by weight of acetic acid and 0.2 partby weight of CoCl (previously dissolved in the acetic acid) is introduced into the reaction-vessel-and oxidation is carried out after the manner described in Example 1,-for a period of .65 minutes at a temperature of 85 C.
- the resultant mixture contains less than 1%. of peroxide, in addition to the unreacted indane and indanone After elimination of such acetic acid as may be present and distillation of the unreacted indane, indanone-1 is recovered.
- indanone-1 The authenticity of indanone-1 is confirmed inter alia by conversion thereof into 2-4-dinitrophenylhydrazone and by its refractive index. The yield of indanone relative to the reacted indane is 69% 1
- Example 7 There are recovered parts by weight of unreacted acenaphthene and 70 parts by weight of acenaphthenone. The authenticity of acenaphthenone is confirmed inter alia by conversion thereof into the oxime and the 2-4-dinitrophenylhydrazone.
- Example 8 A mixture of 336 parts by weight of diphenylmethane,
- T 118.5 parts by weight of acetic acid, and 0.2 part by weight of CoCl (preliminarily dissolved in the acetic acid) is introduced into the reaction vessel, and oxidation carried out as described in Example 1, except that a temperature'of is employed and the treating period is 'extended to 65 minutes.
- T heresultant mixture contains less than 0.8% of peroxide, in addition to unreacted diphenyl-' methane and benzophenone.
- the benzophenone is separated by precipitation thereof in the form of its oxime, and the unreacted diphenyl methane is distilled ofi.
- the particularly employed acid solvent may just as well be replaced byanother monobasic organic acid solvent.
- acetic acid it may be'replaced by propionic acid or butyric acid or the like, and vice versa.
- the particular oxidation catalyst therein employed may as well be replaced by equivalent quantities of other of the hereinbeforedescribed oxidation catalysts, such as for example the'cations of such metals as vanadium, chromium, manganese,- copper, zinc, silver, tin, antimony, lead, bismuth, iron,
- the acid solvent which is employed according to the present invention is not only a solvent for the oxidation catalyst but also for the hydrocarbon being oxidized.
- the oxidation catalysts are per se conventional, i. e. are known oxidation catalysts.
- the combination catalyst-solvent has a specific chemical effect since it secures the selectivity of the reaction and therefore the solvent is not to be considered only for its physical properties.
- a lower alkanoic acid solvent and of an oxidation catalyst said catalyst being formed by dissolving in the lower alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
- a lower alkanoic acid solvent and of an oxidation catalyst said catalyst being formed by dissolving in the lower alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
- oxidation catalyst in the presence of an oxidation catalyst and of an alkanoic acid solvent in a molar proportion of 1 to 20 relative to the hydrocarbon, said oxidation catalyst being formed by dissolving in the alkanoic acid solvent a member selected from the group consisting of a metal, a metal oxide, a metal salt, and a metal soap, whereby the said binuclear hydrocarbon is selectively oxidized to the desired bicyclic ketone and the formation of undesired byproducts is suppressed.
- tetralone which comprises dissolving Tetralin and cobalt chloride in acetic acid and bubbling an oxygen-containing gas through said solution at a temperature of from about 80 to 200 C.
- indanone which comprises dissolving indane and cobalt chloride in acetic acid and bubbling an oxygen-containing gas' through said solution at a temperature of from about 80 to 200 C.
- acenaphthenone which comprises dissolving acenaphthene and cobalt chloride in butyric acid and bubbling an oxygen-containing gas through said solution at a temperature of from about 80 to 200 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US470797A US2859247A (en) | 1954-11-23 | 1954-11-23 | Process for the preparation of bicyclic ketones |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US470797A US2859247A (en) | 1954-11-23 | 1954-11-23 | Process for the preparation of bicyclic ketones |
| GB34387/54A GB770478A (en) | 1954-11-26 | 1954-11-26 | An improved process of producing polycyclic ketones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2859247A true US2859247A (en) | 1958-11-04 |
Family
ID=10365016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US470797A Expired - Lifetime US2859247A (en) | 1954-11-23 | 1954-11-23 | Process for the preparation of bicyclic ketones |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2859247A (en, 2012) |
| BE (1) | BE533179A (en, 2012) |
| DE (1) | DE1044059B (en, 2012) |
| FR (1) | FR1095348A (en, 2012) |
| GB (1) | GB770478A (en, 2012) |
| NL (1) | NL91100C (en, 2012) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2977310A (en) * | 1957-04-17 | 1961-03-28 | Sun Oil Co | Oxidation of petroleum fractions |
| US3038940A (en) * | 1958-04-25 | 1962-06-12 | Standard Oil Co | Process for preparation of aromatic ketones |
| DE1212508B (de) * | 1962-06-13 | 1966-03-17 | United States Steel Corp | Verfahren zur katalytischen Oxydation von teilweise hydrierten, polycyclischen, aromatischen und heterocyclischen Verbindungen |
| US3310586A (en) * | 1963-02-14 | 1967-03-21 | Gen Electric | Process of making 3, 4-dihydro-1(2h)-naphthalenones |
| US3855252A (en) * | 1968-07-15 | 1974-12-17 | Ashland Oil Inc | Liquid phase oxidation of condensed-ring aromatic hydrocarbons |
| US4146582A (en) * | 1976-01-30 | 1979-03-27 | Brichima S.P.A. | Process for preparing aromatic aldehydes and ketones |
| US4175098A (en) * | 1977-07-07 | 1979-11-20 | Director-General Of The Agency Of Industrial Science And Technology | Method for the preparation of α-tetralone |
| US4405523A (en) * | 1982-03-24 | 1983-09-20 | Standard Oil Company (Indiana) | Process for preparation of benzophenone, anthraquinone and O-dibenzoylbenzene |
| EP0162465A3 (en) * | 1984-05-24 | 1987-02-25 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Novel compounds useful in perfumes |
| US5015778A (en) * | 1989-12-18 | 1991-05-14 | The Dow Chemical Company | Catalytic method to produce hydroxy substituted arylophenones |
| WO2022085746A1 (ja) * | 2020-10-23 | 2022-04-28 | 三菱瓦斯化学株式会社 | フルオレノンの製造方法 |
| WO2023054644A1 (ja) * | 2021-10-01 | 2023-04-06 | 三菱瓦斯化学株式会社 | フルオレノンの製造方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3424789A (en) * | 1964-03-05 | 1969-01-28 | Gulf Research Development Co | Process for oxidizing a 1,1-bis-(alkyl-phenyl)alkane |
| DE1267675B (de) * | 1966-07-28 | 1968-05-09 | Akad Wissenschaften Ddr | Verfahren zur Herstellung von p-Nitroacetophenon durch Oxydation von p-Nitroaethylbenzol mit Sauerstoff oder Luft |
| CN102584557B (zh) * | 2011-12-31 | 2014-03-26 | 浙江工业大学 | 一种苊酮的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2245528A (en) * | 1938-10-18 | 1941-06-10 | Du Pont | Catalytic oxidation of alkyl substituted aromatic compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1813606A (en) * | 1926-12-23 | 1931-07-07 | Ig Farbenindustrie Ag | Process of obtaining oxygenated compounds from alkyl benzenes |
| DE767389C (de) * | 1940-11-16 | 1952-07-31 | Bayer Ag | Verfahren zur Herstellung von Diketonen |
-
1953
- 1953-10-23 FR FR1095348D patent/FR1095348A/fr not_active Expired
-
1954
- 1954-11-02 BE BE533179D patent/BE533179A/xx unknown
- 1954-11-10 DE DEI9354A patent/DE1044059B/de active Pending
- 1954-11-23 US US470797A patent/US2859247A/en not_active Expired - Lifetime
- 1954-11-25 NL NL192671D patent/NL91100C/xx active
- 1954-11-26 GB GB34387/54A patent/GB770478A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2245528A (en) * | 1938-10-18 | 1941-06-10 | Du Pont | Catalytic oxidation of alkyl substituted aromatic compounds |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2977310A (en) * | 1957-04-17 | 1961-03-28 | Sun Oil Co | Oxidation of petroleum fractions |
| US3038940A (en) * | 1958-04-25 | 1962-06-12 | Standard Oil Co | Process for preparation of aromatic ketones |
| DE1212508B (de) * | 1962-06-13 | 1966-03-17 | United States Steel Corp | Verfahren zur katalytischen Oxydation von teilweise hydrierten, polycyclischen, aromatischen und heterocyclischen Verbindungen |
| US3310586A (en) * | 1963-02-14 | 1967-03-21 | Gen Electric | Process of making 3, 4-dihydro-1(2h)-naphthalenones |
| US3855252A (en) * | 1968-07-15 | 1974-12-17 | Ashland Oil Inc | Liquid phase oxidation of condensed-ring aromatic hydrocarbons |
| US4146582A (en) * | 1976-01-30 | 1979-03-27 | Brichima S.P.A. | Process for preparing aromatic aldehydes and ketones |
| US4175098A (en) * | 1977-07-07 | 1979-11-20 | Director-General Of The Agency Of Industrial Science And Technology | Method for the preparation of α-tetralone |
| US4405523A (en) * | 1982-03-24 | 1983-09-20 | Standard Oil Company (Indiana) | Process for preparation of benzophenone, anthraquinone and O-dibenzoylbenzene |
| EP0162465A3 (en) * | 1984-05-24 | 1987-02-25 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Novel compounds useful in perfumes |
| US5015778A (en) * | 1989-12-18 | 1991-05-14 | The Dow Chemical Company | Catalytic method to produce hydroxy substituted arylophenones |
| WO2022085746A1 (ja) * | 2020-10-23 | 2022-04-28 | 三菱瓦斯化学株式会社 | フルオレノンの製造方法 |
| JPWO2022085746A1 (en, 2012) * | 2020-10-23 | 2022-04-28 | ||
| CN116323538A (zh) * | 2020-10-23 | 2023-06-23 | 三菱瓦斯化学株式会社 | 芴酮的制造方法 |
| WO2023054644A1 (ja) * | 2021-10-01 | 2023-04-06 | 三菱瓦斯化学株式会社 | フルオレノンの製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1044059B (de) | 1958-11-20 |
| NL91100C (en, 2012) | 1959-06-15 |
| BE533179A (en, 2012) | 1954-11-30 |
| FR1095348A (fr) | 1955-06-01 |
| GB770478A (en) | 1957-03-20 |
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